Hole transport materials

ABSTRACT

There is provided a hole transport polymer having a carbazole group and an amino nitrogen having Formula I 
     
       
         
         
             
             
         
       
     
     In the formula: Ar 1 , Ar 2 , and Ar 4  are the same or different and are substituted or unsubstituted aryl groups or deuterated aryl groups; Ar 3  is substituted or unsubstituted aryl groups or deuterated aryl groups; E is the same or different at each occurrence and is selected from the group consisting of H, D, halide, alkyl, aryl, siloxane, deuterated alkyl, deuterated aryl, deuterated siloxane, and a crosslinking group; R 1 -R 2  are the same or different at each occurrence and are selected from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl, deuterated partially-fluorinated alkyl, deuterated aryl, deuterated heteroaryl, deuterated amino, deuterated silyl, deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy, and crosslinking groups, wherein adjacent groups selected from R 1  and R 2  can be joined together to form a fused ring; a is an integer from 0-4; b is an integer from 0-3; and n is an integer greater than or equal to 1.

RELATED APPLICATION DATA

This application claims the benefit of U.S. Provisional Application No.62/082,232 filed on Nov. 20, 2014; U.S. Provisional Application No.62/157,531 filed on May 6, 2015; and U.S. Provisional Application No.62/251,405 filed on Nov. 5, 2015 ; all of which are incorporated byreference herein in their entirety.

BACKGROUND INFORMATION Field of the Disclosure

The present disclosure relates to novel hole transport compounds. Thedisclosure further relates to electronic devices having at least onelayer comprising such an hole transport compound.

Description of the Related Art

In organic electronic devices, such as organic light emitting diodes(“OLED”), that make up OLED displays, one or more organic electroactivelayers are sandwiched between two electrical contact layers. In an OLEDat least one organic electroactive layer emits light through thelight-transmitting electrical contact layer upon application of avoltage across the electrical contact layers.

It is well known to use organic electroluminescent compounds as thelight-emitting component in light-emitting diodes. Simple organicmolecules, conjugated polymers, and organometallic complexes have beenused.

Devices that use electroluminescent materials frequently include one ormore charge transport layers, which are positioned between a photoactive(e.g., light-emitting) layer and a contact layer (hole-injecting contactlayer). A device can contain two or more contact layers. A holetransport layer can be positioned between the photoactive layer and thehole-injecting contact layer. The hole-injecting contact layer may alsobe called the anode. An electron transport layer can be positionedbetween the photoactive layer and the electron-injecting contact layer.The electron-injecting contact layer may also be called the cathode.

There is a continuing need for electroactive materials for use inelectronic devices.

SUMMARY

There is provided a hole transport polymer having a carbazole group andan amino nitrogen, wherein said polymer has Formula I

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated alkoxy, deuterated ester,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to1.

There is also provided a monomer having a carbazole group and an aminonitrogen, wherein said monomer has Formula Ia

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy,        ester, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

There is also provided a hole transport polymer having a carbazole groupand an amino nitrogen, wherein said polymer has Formula II

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester, deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to1.

There is also provided a monomer having a carbazole group and an aminonitrogen, wherein said monomer has Formula IIa

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

There is also provided a hole transport copolymer having Formula III

wherein:

-   -   A is a monomeric unit having Formula Ia or Formula IIa;    -   B is a monomeric unit having at least three points of attachment        in the copolymer;    -   C is an aromatic monomeric unit or a deuterated analog thereof;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        arylamino, siloxane, ester, crosslinkable groups, deuterated        alkyl, deuterated aryl, deuterated arylamino, deuterated        siloxane, deuterated ester, and deuterated crosslinkable groups;    -   x, y, and z are the same or different and are mole fractions,        such that x+y+z=1, and x and y are non-zero.

There is also provided an electronic device having at least one layercomprising a polymer of Formula I, Formula II, or a copolymer of FormulaIII.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of one example of an organic electronicdevice including the new hole transport polymer or copolymer describedherein.

FIG. 2 includes an illustration of another example of an organicelectronic device including the new hole transport polymer or copolymerdescribed herein.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

There is provided a hole transport polymer having a carbazole group andan amino nitrogen, wherein said polymer has Formula I

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester, deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated alkoxy, deuterated aryloxy,        deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy,        deuterated ester, and crosslinking groups, wherein adjacent        groups selected from R¹ and R² can be joined together to form a        fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to 1.

There is also provided a monomer having a carbazole group and an aminonitrogen, wherein said monomer has Formula Ia

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

There is also provided a hole transport polymer having a carbazole groupand an amino nitrogen, wherein said polymer has Formula II

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester, deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy,        aryloxy, fluoroalkoxy, siloxane, siloxy, ester, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated alkoxy, deuterated aryloxy,        deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy,        deuterated ester, and crosslinking groups, wherein adjacent        groups selected from R¹ and R² can be joined together to form a        fused ring;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to1.

There is also provided a monomer having a carbazole group and an aminonitrogen, wherein said monomer has Formula IIa

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

There is also provided a hole transport copolymer having Formula III

wherein:

-   -   A is a monomeric unit having Formula Ia or Formula IIa;    -   B is a monomeric unit having at least three points of attachment        in the copolymer;    -   C is an aromatic monomeric unit or a deuterated analog thereof;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        arylamino, siloxane, ester, crosslinkable groups, deuterated        alkyl, deuterated aryl, deuterated arylamino, deuterated        siloxane, deuterated ester, and deuterated crosslinkable groups;    -   x, y, and z are the same or different and are mole fractions,        such that x+y+z=1, and x and y are non-zero.

There is also provided an electronic device having at least one layercomprising a polymer of Formula I, Formula II, or a copolymer of FormulaIII.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description and from the claims.The detailed description first addresses Definitions and Clarificationof Terms, followed by the Compound, the Electronic Device, and finallyExamples.

1 Definitions and Clarification of Terms

Before addressing details of embodiments described below, some terms aredefined or clarified.

As used herein, the term “adjacent” as it refers to substituent groupsrefers to groups that are bonded to carbons that are joined togetherwith a single or multiple bond. Exemplary adjacent R groups are shownbelow:

The term “alkoxy” is intended to mean the group RO-x, where R is analkyl group.

The term “alkyl” includes branched and straight-chain saturatedaliphatic hydrocarbon groups. Unless otherwise indicated, the term isalso intended to include cyclic groups. Examples of alkyl groups includemethyl, ethyl, propyl, isopropyl, isobutyl, secbutyl, tertbutyl, pentyl,isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl and thelike. The term “alkyl” further includes both substituted andunsubstituted hydrocarbon groups. In some embodiments, the alkyl groupmay be mono-, di- and tri-substituted. One example of a substitutedalkyl group is trifluoromethyl. Other substituted alkyl groups areformed from one or more of the substituents described herein. In certainembodiments alkyl groups have 1 to 20 carbon atoms. In otherembodiments, the group has 1 to 6 carbon atoms. The term is intended toinclude heteroalkyl groups. Heteroalkyl groups may have from 1-20 carbonatoms.

The term “amino group” is intended to mean the group —NR₂, where R isthe same or different at each occurrence and can be an alkyl group, anaryl group, or deuterated analogs thereof.

The term “aromatic compound” is intended to mean an organic compoundcomprising at least one unsaturated cyclic group having delocalized pielectrons. The term is intended to encompass both aromatic compoundshaving only carbon and hydrogen atoms, and heteroaromatic compoundswherein one or more of the carbon atoms within the cyclic group has beenreplaced by another atom, such as nitrogen, oxygen, sulfur, or the like.

The term “aryl” or “aryl group” means a moiety derived from an aromaticcompound. A group “derived from” a compound, indicates the radicalformed by removal of one or more H or D. The aryl group may be a singlering (monocyclic) or multiple rings (bicyclic, or more) fused togetheror linked covalently. Examples of aryl moieties include, but are notlimited to, phenyl, 1-naphthyl, 2-naphthyl, dihydronaphthyl,tetrahydronaphthyl, biphenyl. anthryl, phenanthryl, fluorenyl, indanyl,biphenylenyl, acenaphthenyl, acenaphthylenyl, and the like. In someembodiments, aryl groups have 6 to 60 ring carbon atoms; in someembodiments, 6 to 30 ring carbon atoms. The term is intended to includehydrocarbon aryls, having only carbon atoms and hydrogen atoms; andheteroaryls, having at least one heteroatom in one or more of the rings.Heteroaryl groups may have from 4-50 ring carbon atoms; in someembodiments, 4-30 ring carbon atoms.

The term “aryloxy” is intended to mean the group —OR, where R is aryl.

The term “charge transport,” when referring to a layer, material,member, or structure is intended to mean such layer, material, member,or structure facilitates migration of such charge through the thicknessof such layer, material, member, or structure with relative efficiencyand small loss of charge. Hole transport materials facilitate positivecharge; electron transport materials facilitate negative charge.Although light-emitting materials may also have some charge transportproperties, the term “charge transport layer, material, member, orstructure” is not intended to include a layer, material, member, orstructure whose primary function is light emission.

The term “compound” is intended to mean an electrically unchargedsubstance made up of molecules that further include atoms, wherein theatoms cannot be separated from their corresponding molecules by physicalmeans without breaking chemical bonds. The term is intended to includeoligomers and polymers.

The term “crosslinkable group” or “crosslinking group” is intended tomean a group on a compound or polymer chain than can link to anothercompound or polymer chain via thermal treatment, use of an initiator, orexposure to radiation, where the link is a covalent bond. In someembodiments, the radiation is UV or visible. Examples of crosslinkablegroups include, but are not limited to vinyl, acrylate,perfluorovinylether, 1-benzo-3,4-cyclobutane, o-quinodimethane groups,siloxane, cyanate groups, cyclic ethers (epoxides), internal alkenes(e.g., stillbene) cycloalkenes, and acetylenic groups.

The term “electroactive” as it refers to a layer or a material, isintended to indicate a layer or material which electronicallyfacilitates the operation of the device. Examples of electroactivematerials include, but are not limited to, materials which conduct,inject, transport, or block a charge, where the charge can be either anelectron or a hole, or materials which emit radiation or exhibit achange in concentration of electron-hole pairs when receiving radiation.Examples of inactive materials include, but are not limited to,planarization materials, insulating materials, and environmental barriermaterials.

The prefix “fluoro” is intended to indicate that one or more hydrogensin a group has been replaced with fluorine.

The prefix “hetero” indicates that one or more carbon atoms has beenreplaced with a different atom. In some embodiments, the heteroatom isO, N, S, or combinations thereof.

The term “liquid composition” is intended to mean a liquid medium inwhich a material is dissolved to form a solution, a liquid medium inwhich a material is dispersed to form a dispersion, or a liquid mediumin which a material is suspended to form a suspension or an emulsion.The term “molecular weight” (of polymer with “n” repeat units) isintended to mean the total mass of a polymeric molecule and iscalculated as the sum of the mass of each constituent atom multiplied bythe number of atoms of that element in the polymeric formula. Thepractical upper limit of n is determined in part by the desiredsolubility of a compound in a particular solvent or class of solvents.As the value of n increases, the molecular weight of the compoundincreases.

The term “monomeric unit” is intended to mean a repeating unit in apolymer. It represents the largest constitutional unit contributed by asingle monomer to the structure of a polymer.

The term “photoactive” refers to a material or layer that emits lightwhen activated by an applied voltage (such as in a light emitting diodeor chemical cell), that emits light after the absorption of photons(such as in down-converting phosphor devices), or that responds toradiant energy and generates a signal with or without an applied biasvoltage (such as in a photodetector or a photovoltaic cell).

The term “polymer” is intended to mean a material having at least onerepeating monomeric unit. The term includes homopolymers having only onekind of monomeric unit, and copolymers having two or more differentmonomeric units. Copolymers are a subset of polymers.

The term “siloxane” refers to the group R₃SiOR₂Si—, where R is the sameor different at each occurrence and is H, D, C₁₋₂₀ alkyl, deuteratedalkyl, fluoroalkyl, aryl, or deuterated aryl. In some embodiments, oneor more carbons in an R alkyl group are replaced with Si. The term“siloxy” refers to to the group R₃SiO—, where R is the same or differentat each occurrence and is H, D, C₁₋₂₀ alkyl, deuterated alkyl,fluoroalkyl, aryl, or deuterated aryl.

The term “silyl” refers to the group R₃Si—, where R is the same ordifferent at each occurrence and is H, D, C₁₋₂₀ alkyl, deuterated alkyl,fluoroalkyl, aryl, or deuterated aryl. In some embodiments, one or morecarbons in an R alkyl group are replaced with Si.

Unless otherwise indicated, all groups can be substituted orunsubstituted. An optionally substituted group, such as, but not limitedto, alkyl or aryl, may be substituted with one or more substituentswhich may be the same or different. Suitable substituents include D,alkyl, aryl, nitro, cyano, —N(R′)(R″), halo, hydroxy, carboxy, alkenyl,alkynyl, cycloalkyl, heteroaryl, alkoxy, aryloxy, heteroaryloxy,alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl, silyl,siloxane, thioalkoxy, —S(O)₂—N(R′)(R″), —C(═O)—N(R′)(R″),(R′)(R″)N-alkyl, (R′)(R″)N-alkoxyalkyl, (R′)(R″)N-alkylaryloxyalkyl,—S(O)_(s)-aryl (where s=0−2) or —S(O)_(s)—heteroaryl (where s=0−2). EachR′ and R″ is independently an optionally substituted alkyl, cycloalkyl,or aryl group. R′ and R″, together with the nitrogen atom to which theyare bound, can form a ring system in certain embodiments. Substituentsmay also be crosslinking groups.

In a structure where a substituent bond passes through one or more ringsas shown below,

it is meant that the substituent R may be bonded at any availableposition on the one or more rings.

In this specification, unless explicitly stated otherwise or indicatedto the contrary by the context of usage, where an embodiment of thesubject matter hereof is stated or described as comprising, including,containing, having, being composed of or being constituted by or ofcertain features or elements, one or more features or elements inaddition to those explicitly stated or described may be present in theembodiment. An alternative embodiment of the disclosed subject matterhereof, is described as consisting essentially of certain features orelements, in which embodiment features or elements that would materiallyalter the principle of operation or the distinguishing characteristicsof the embodiment are not present therein. A further alternativeembodiment of the described subject matter hereof is described asconsisting of certain features or elements, in which embodiment, or ininsubstantial variations thereof, only the features or elementsspecifically stated or described are present.

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

In this specification, unless explicitly stated otherwise or indicatedto the contrary by the context of usage, chemical and structuralformulae may be depicted using the line-angle formula convention. In aline-angle formula, bonds are represented by lines, and carbon atoms areassumed to be present wherever two lines meet or a line begins or ends.Nitrogen, oxygen, halogens, and other heteroatoms are shown; buthydrogen atoms are not usually drawn when bonded to carbon. Each sp³carbon atom is assumed to have enough bonded hydrogen atoms in order togive it a total of four bonds; each sp² carbon, three bonds; each spcarbon, two bonds. The depiction of Formula I herein is an example ofthe use of the line-angle formula convention.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2a. Hole Transport Polymer Having Formula I

The hole transport polymer having a carbazole group and an aminonitrogen described herein has Formula I

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester, deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy,        ester, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated alkoxy, deuterated ester,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to 1.

As used herein, the term “hole transport polymer having a carbazolegroup and an amino nitrogen having Formula I” is intended to designate apolymer based on a repeat unit, or monomer, as defined by Formula I.Polymerization sites are the aryl halide groups attached to the nitrogencenters (amine and carbazole) within each monomer. This class ofmaterials leads to monomers of AB type and generates polymeric holetransport films with a random distribution of AA, BB, and AB segmentsthroughout the polymer. This can result in differential degrees ofnon-associative packing that ultimately determines the associatedfilm-forming properties. In some embodiments, the distribution ofmonomeric segments can be manipulated so as to optimize properties ofcompounds having Formula I for use in electronic devices.

In some embodiments, the compound having Formula I is deuterated. Theterm “deuterated” is intended to mean that at least one

H has been replaced by deuterium (“D”). The term “deuterated analog”refers to a structural analog of a compound or group in which one ormore available hydrogens have been replaced with deuterium. In adeuterated compound or deuterated analog, the deuterium is present in atleast 100 times the natural abundance level. In some embodiments, thecompound is at least 10% deuterated. By “% deuterated” or “%deuteration” is meant the ratio of deuterons to the sum of protons plusdeuterons, expressed as a percentage. In some embodiments, the compoundis at least 10% deuterated; in some embodiments, at least 20%deuterated; in some embodiments, at least 30% deuterated; in someembodiments, at least 40% deuterated; in some embodiments, at least 50%deuterated; in some embodiments, at least 60% deuterated; in someembodiments, at least 70% deuterated; in some embodiments, at least 80%deuterated; in some embodiments, at least 90% deuterated; in someembodiments, 100% deuterated.

Deuterated materials can be less susceptible to degradation by holes,electrons, excitons, or a combination thereof. Deuteration canpotentially inhibit degradation of the compound during device operation,which in turn can lead to improved device lifetime. In general, thisimprovement is accomplished without sacrificing other device properties.Furthermore, the deuterated compounds frequently have greater airtolerance than the non-deuterated analogs. This can result in greaterprocessing tolerance both for the preparation and purification of thematerials and in the formation of electronic devices using thematerials.

In some embodiments of Formula I, n=1.

In some embodiments of Formula I, n=2-5.

In some embodiments of Formula I, n>5.

In some embodiments of Formula I, n=6-10.

In some embodiments of Formula I, the compound is a polymer with n>10.In some embodiments of Formula I, the compound is a polymer with n>100.In some embodiments, the compound is a polymer with M_(n)>20,000; insome embodiments, M_(n)>50,000; in some embodiments, M_(n)>100,000; insome embodiments, M_(n)>150,000.

In some embodiments of Formula I, E is H or D.

In some embodiments of Formula I, E is D.

In some embodiments of Formula I, E is a halogen. In some embodimentsthe halogen is CI or Br; in some embodiments, Br.

In some embodiments of Formula I, E is an aryl or deuterated aryl group;in some embodiments the aryl group is substituted; in some embodiments,the aryl group is unsubstituted.

In some embodiments of Formula I, E is a monocyclic aryl group ordeuterated monocyclic aryl group.

In some embodiments of Formula I, E is an aryl group with multiple ringsfused together. In some embodiments the multiple rings fused togetherinclude deuterium.

In some embodiments of Formula I, E is a heteroaryl group or deuteratedheteroaryl group.

In some embodiments of Formula I, E is a siloxane group or deuteratedsiloxane group.

In some embodiments of Formula I, E is an ester or deuterated ester.

In some embodiments of Formula I, E is further substituted withadditional groups that may or may not include deuterium.

In some embodiments of Formula I, E is a crosslinking group.

In some embodiments, one or more of Ar¹-Ar⁴ is an aryl group having atleast one fused ring.

In some embodiments, one or more of Ar¹-Ar⁴ is selected from the groupconsisting of naphthyl, anthracenyl, naphthylphenyl, phenylnaphthyl,fluorenyl, substituted derivatives thereof, and deuterated analogsthereof.

In some embodiments of Formula I, Ar¹-Ar⁴ are aryl groups having nofused rings.

In some embodiments of Formula I, Ar¹-Ar⁴ are aryl groups that arefurther substituted with additional groups that may or may not includedeuterium.

In some embodiments of Formula I, Ar¹-Ar⁴ are hydrocarbon aryl groups.

In some embodiments of Formula I, Ar¹-Ar⁴ are heteroaryl groups.

In some embodiments of Formula I, Ar¹-Ar⁴ are both hydrocarbon arylgroups and heteroaryl groups.

In some embodiments of Formula I, Ar¹ has Formula a

where:

R⁹ is the same or different at each occurrence and is selected from thegroup consisting of D, alkyl, alkoxy, siloxane and silyl, whereinadjacent R⁹ groups can be joined together to form a fused ring;

-   -   p is the same or different at each occurrence and is an integer        from 0-4;    -   r is an integer from 1 to 5; and    -   *indicates the point of attachment to E.

In some embodiments, Ar¹ has Formula b

where R⁹, p, r and * are as in Formula a.

In some embodiments of Formula I, Ar¹ has Formula c

where R⁹, p, r and * are as in Formula a.

In some embodiments of Formula I, Ar¹ is selected from the groupconsisting of 1-naphthyl, 2-naphthyl, anthracenyl, fluorenyl, deuteratedanalogs thereof, and derivatives thereof having one or more substituentsselected from the group consisting of fluoro, alkyl, alkoxy, silyl,siloxy, a substituent with a crosslinking group, and deuterated analogsthereof.

In some embodiments of Formula I, Ar⁴ has Formula a.

In some embodiments of Formula I, Ar⁴ has Formula b.

In some embodiments of Formula I, Ar⁴ has Formula c.

In some embodiments of Formula I, Ar⁴ is selected from the groupconsisting of 1-naphthyl, 2-naphthyl, anthracenyl, fluorenyl, deuteratedanalogs thereof, and derivatives thereof having one or more substituentsselected from the group consisting of fluoro, alkyl, alkoxy, silyl,siloxy, a substituent with a crosslinking group, and deuterated analogsthereof.

In some embodiments of Formula a-c, at least one p is not zero.

In some embodiments of Formula a-c, r=1-3.

In some embodiments of Formula I, Ar¹═Ar⁴.

In some embodiments of Formula I, Ar¹ and Ar⁴ are selected from thegroup consisting of phenyl, biphenyl, terphenyl, deuterated analogsthereof, and derivatives thereof having one or more substituentsselected from the group consisting of fluoro, alkyl, alkoxy, silyl,siloxy, a substituent with a crosslinking group, and deuterated analogsthereof.

In some embodiments of Formula I, Ar² has Formula a′

where:

-   -   R⁹ is the same or different at each occurrence and is selected        from the group consisting of D, alkyl, alkoxy, siloxane and        silyl, wherein adjacent R⁹ groups can be joined together to form        a fused ring;    -   p is the same or different at each occurrence and is an integer        from 0-4;    -   r is an integer from 1 to 5; and    -   * indicates the point of attachment to the amino-Nitrogen atom;    -   ** indicates the point of attachment to the aromatic ring of the        carbazole.

In some embodiments, Ar² has Formula b′

where R⁹, p, r, *, and ** are as in Formula a′.

In some embodiments of Formula I, Ar² has Formula c′

where R⁹, p, r, *, and ** are as in Formula a′.

In some embodiments of Formula I, Ar² is selected from the groupconsisting of 1-naphthyl, 2-naphthyl, anthracenyl, fluorenyl, deuteratedanalogs thereof, and derivatives thereof having one or more substituentsselected from the group consisting of fluoro, alkyl, alkoxy, silyl,siloxy, a substituent with a crosslinking group, and deuterated analogsthereof.

In some embodiments of Formulae a′-c′, at least one p is not zero.

In some embodiments of Formulae a′-c′, r=1-3.

In some embodiments of Formula I, Ar³ has Formula d

where:

-   -   R⁹ is the same or different at each occurrence and is selected        from the group consisting of D, alkyl, alkoxy, siloxane and        silyl,    -   wherein adjacent R⁹ groups can be joined together to form a        fused ring;    -   p is the same or different at each occurrence and is an integer        from 0-4;    -   q is an integer from 0-5; and    -   r is an integer from 1 to 5.

In some embodiments of Formula I, Ar³ has Formula e

where R⁹, p, and, r are as in Formula d.

In some embodiments of Formula I, Ar³ has Formula f

where R⁹, p, and, r are as in Formula d.

In some embodiments of Formula I, Ar³ is selected from the groupconsisting of 1-naphthyl, 2-naphthyl, anthracenyl, fluorenyl, deuteratedanalogs thereof, and derivatives thereof having one or more substituentsselected from the group consisting of fluoro, alkyl, alkoxy, silyl,siloxy, a substituent with a crosslinking group, and deuterated analogsthereof.

In some embodiments of Formula I, a=0.

In some embodiments of Formula I, a=1.

In some embodiments of Formula I, a=2.

In some embodiments of Formula I, a=3.

In some embodiments of Formula I, a=4.

In some embodiments of Formula I, a>0 and R¹ is D or C₁₋₁₀ alkyl. Insome embodiments, the alkyl group is deuterated.

In some embodiments of Formula I, a>0 and R¹ is C₁₋₁₀ silyl. In someembodiments, the silyl group is deuterated.

In some embodiments of Formula I, a>0 and R¹ is a germyl group. In someembodiments, the germyl group is deuterated.

In some embodiments of Formula I, a>0 and R¹ is an ester group. In someembodiments, the ester group is deuterated.

In some embodiments of Formula I, a>0 and R¹ is C₆₋₂₀ aryl or C₆₋₂₀deuterated aryl. In some embodiments, the aryl group is a hydrocarbonaryl. In some embodiments, the aryl is a heteroaryl.

In some embodiments of Formula I, a>0 and R¹ is an amino group. In someembodiments, the amino group is deuterated.

In some embodiments of Formula I, a=4 and R¹=D.

In some embodiments of Formula I, R¹ and R² are the same.

In some embodiments of Formula I, R¹ and R² are different.

In some embodiments of Formula I, b=0.

In some embodiments of Formula I, b=1.

In some embodiments of Formula I, b=2.

In some embodiments of Formula I, b=3.

In some embodiments of Formula I, b>0 and R² is D or C₁₋₁₀ alkyl. Insome embodiments, the alkyl group is deuterated.

In some embodiments of Formula I, b>0 and R² is C₁₋₁₀ silyl. In someembodiments, the silyl group is deuterated.

In some embodiments of Formula I, b>0 and R² is a germyl group. In someembodiments, the germyl group is deuterated.

In some embodiments of Formula I, b>0 and R² is a ester group.

In some embodiments, the ester group is deuterated.

In some embodiments of Formula I, b>0 and R² is C₆₋₂₀ aryl or C₆₋₂₀deuterated aryl. In some embodiments, the aryl group is a hydrocarbonaryl. In some embodiments, the aryl is a heteroaryl.

In some embodiments of Formula I, b=3 and R¹=D.

Any of the above embodiments for Formula I can be combined with one ormore of the other embodiments, so long as they are not mutuallyexclusive. For example, the embodiment in which Ar¹═Ar⁴ can be combinedwith the embodiment in which E=D. The same is true for the othernon-mutually-exclusive embodiments discussed above. The skilled personwould understand which embodiments were mutually exclusive and wouldthus readily be able to determine the combinations of embodiments thatare contemplated by the present application.

Some non-limiting examples of compounds having Formula I are shownbelow.

2b. Monomer Having Formula Ia

The monomer described herein has Formula Ia

wherein:

-   -   Ar¹, Ar², and Ar⁴ are the same or different and are substituted        or unsubstituted aryl groups or deuterated aryl groups;    -   Ar³ is substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, ester, silyl, germyl,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated ester,        deuterated silyl, deuterated germyl, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   a is an integer from 0-4;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

As used herein, the term “monomer having Formula Ia” is intended todesignate a polymer repeat unit, or monomer, as defined by Formula Ia.Polymerization sites are designated “#” in Formula Ia. The class ofpolymeric materials generated from monomers of this type producespolymeric hole transport films with a random distribution of AA, BB, andAB segments throughout the polymer. This can result in differentialdegrees of non-associative packing that ultimately determines theassociated film-forming properties. In some embodiments, thedistribution of monomeric segments can be manipulated so as to optimizeproperties of polymers made from monomers having Formula Ia for use inelectronic devices.

In some embodiments, the monomer having Formula Ia is deuterated. Theterm “deuterated” is intended to mean that at least one H has beenreplaced by deuterium (“D”). The term “deuterated analog” refers to astructural analog of a compound or group in which one or more availablehydrogens have been replaced with deuterium. In a deuterated compound ordeuterated analog, the deuterium is present in at least 100 times thenatural abundance level. In some embodiments, the compound is at least10% deuterated. By “% deuterated” or “% deuteration” is meant the ratioof deuterons to the sum of protons plus deuterons, expressed as apercentage. In some embodiments, the monomer is at least 10% deuterated;in some embodiments, at least 20% deuterated; in some embodiments, atleast 30% deuterated; in some embodiments, at least 40% deuterated; insome embodiments, at least 50% deuterated; in some embodiments, at least60% deuterated; in some embodiments, at least 70% deuterated; in someembodiments, at least 80% deuterated; in some embodiments, at least 90%deuterated; in some embodiments, 100% deuterated.

Deuterated materials can be less susceptible to degradation by holes,electrons, excitons, or a combination thereof. Deuteration canpotentially inhibit degradation of the compound during device operation,which in turn can lead to improved device lifetime. In general, thisimprovement is accomplished without sacrificing other device properties.Furthermore, the deuterated compounds frequently have greater airtolerance than the non-deuterated analogs. This can result in greaterprocessing tolerance both for the preparation and purification of thematerials and in the formation of electronic devices using thematerials.

All of the above embodiments for Ar¹-Ar⁴ regarding the hole transportpolymer having Formula I apply equally well to Ar¹-Ar⁴ in the monomerhaving Formula Ia.

All of the above embodiments regarding the hole transport polymer havingFormula I apply equally well to a in the monomer having Formula Ia.

All of the above embodiments for R¹ regarding the hole transport polymerhaving Formula I apply equally well to R¹ in the monomer having FormulaIa.

All of the above embodiments for b regarding the hole transport polymerhaving Formula I apply equally well to b in the monomer having FormulaIa.

All of the above embodiments for R² regarding the hole transport polymerhaving Formula I apply equally well to R² in the monomer having FormulaIa.

Any of the above embodiments for Formula Ia can be combined with one ormore of the other embodiments, so long as they are not mutuallyexclusive. For example, the embodiment in which Ar¹═Ar⁴ can be combinedwith the embodiment in which R¹=D. The same is true for the othernon-mutually-exclusive embodiments discussed above. The skilled personwould understand which embodiments were mutually exclusive and wouldthus readily be able to determine the combinations of embodiments thatare contemplated by the present application.

Some non-limiting examples of compounds having Formula Ia are shownbelow.

2c. Hole Transport Polymer Having Formula II

The hole transport polymer having a carbazole group and an aminonitrogen described herein has Formula II

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        siloxane, ester, deuterated alkyl, deuterated aryl, deuterated        siloxane, deuterated ester, and a crosslinking group; p1 R¹-R²        are the same or different at each occurrence and are selected        from the group consisting of D, F, CN, alkyl, fluoroalkyl, aryl,        heteroaryl, amino, silyl, germyl, alkoxy, ester, aryloxy,        fluoroalkoxy, siloxane, siloxy, deuterated alkyl, deuterated        partially-fluorinated alkyl, deuterated aryl, deuterated        heteroaryl, deuterated amino, deuterated silyl, deuterated        germyl, deuterated alkoxy, deuterated ester, deuterated aryloxy,        deuterated fluoroalkoxy, deuterated siloxane, deuterated siloxy,        and crosslinking groups, wherein adjacent groups selected from        R¹ and R² can be joined together to form a fused ring;    -   b is an integer from 0-3; and    -   n is an integer greater than or equal to1.

As used herein, the term “hole transport polymer having a carbazolegroup and an amino nitrogen having Formula II” is intended to designatea polymer based on a repeat unit, or monomer, as defined by Formula II.Polymerization sites are the aryl halide groups attached to the nitrogencenters (amine and carbazole) within each monomer. This class ofmaterials leads to monomers of ABC type and generates polymeric holetransport films with a random distribution of AAA, BBB, CCC, and mixedsegments throughout the polymer. This can result in differential degreesof non-associative packing that ultimately determines the associatedfilm-forming properties. In some embodiments, the distribution ofmonomeric segments can be manipulated so as to optimize properties ofcompounds having Formula II for use in electronic devices.

In some embodiments, the compound having Formula II is deuterated. Theterm “deuterated” is intended to mean that at least one H has beenreplaced by deuterium (“D”). The term “deuterated analog” refers to astructural analog of a compound or group in which one or more availablehydrogens have been replaced with deuterium. In a deuterated compound ordeuterated analog, the deuterium is present in at least 100 times thenatural abundance level. In some embodiments, the compound is at least10% deuterated. By “% deuterated” or “% deuteration” is meant the ratioof deuterons to the sum of protons plus deuterons, expressed as apercentage. In some embodiments, the compound is at least 10%deuterated; in some embodiments, at least 20% deuterated; in someembodiments, at least 30% deuterated; in some embodiments, at least 40%deuterated; in some embodiments, at least 50% deuterated; in someembodiments, at least 60% deuterated; in some embodiments, at least 70%deuterated; in some embodiments, at least 80% deuterated; in someembodiments, at least 90% deuterated; in some embodiments, 100%deuterated.

Deuterated materials can be less susceptible to degradation by holes,electrons, excitons, or a combination thereof. Deuteration canpotentially inhibit degradation of the compound during device operation,which in turn can lead to improved device lifetime. In general, thisimprovement is accomplished without sacrificing other device properties.Furthermore, the deuterated compounds frequently have greater airtolerance than the non-deuterated analogs. This can result in greaterprocessing tolerance both for the preparation and purification of thematerials and in the formation of electronic devices using thematerials.

All of the above embodiments for Ar¹-Ar⁴ regarding the hole transportpolymer having Formula I apply equally well to Ar¹-Ar⁴ in the holetransport polymer having Formula II.

All of the above embodiments for Ar² regarding the hole transportpolymer having Formula I apply equally well to Ar^(2a) in the holetransport polymer having Formula II.

All of the above embodiments for Ar³ regarding the hole transportpolymer having Formula I apply equally well to Ar^(3a) in the holetransport polymer having Formula II.

All of the above embodiments for Ar⁴ regarding the hole transportpolymer having Formula I apply equally well to Ar^(4a) in the holetransport polymer having Formula II.

All of the above embodiments for R¹ regarding the hole transport polymerhaving Formula I apply equally well to R¹ in the hole transport polymerhaving Formula II.

All of the above embodiments for b regarding the hole transport polymerhaving Formula I apply equally well to b in the hole transport polymerhaving Formula II.

All of the above embodiments for R² regarding the hole transport polymerhaving Formula I apply equally well to R² in the hole transport polymerhaving Formula II.

Any of the above embodiments for Formula II can be combined with one ormore of the other embodiments, so long as they are not mutuallyexclusive. For example, the embodiment in which Ar¹═Ar⁴ can be combinedwith the embodiment in which R¹=D. The same is true for the othernon-mutually-exclusive embodiments discussed above. The skilled personwould understand which embodiments were mutually exclusive and wouldthus readily be able to determine the combinations of embodiments thatare contemplated by the present application.

Some non-limiting examples of compounds having Formula II are shownbelow.

2d. Monomer Having Formula IIa

The monomer described herein has Formula IIa

wherein:

-   -   Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or different        and are substituted or unsubstituted aryl groups or deuterated        aryl groups;    -   Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups or        deuterated aryl groups;    -   R¹-R² are the same or different at each occurrence and are        selected from the group consisting of D, F, CN, alkyl,        fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,        alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated        alkyl, deuterated partially-fluorinated alkyl, deuterated aryl,        deuterated heteroaryl, deuterated amino, deuterated silyl,        deuterated germyl, deuterated ester, deuterated alkoxy,        deuterated aryloxy, deuterated fluoroalkoxy, deuterated        siloxane, deuterated siloxy, and crosslinking groups, wherein        adjacent groups selected from R¹ and R² can be joined together        to form a fused ring;    -   b is an integer from 0-3; and    -   # is a point of attachment to other monomeric units.

As used herein, the term “monomer having Formula IIa” is intended todesignate a polymer repeat unit, or monomer, as defined by Formula IIa.Polymerization sites are designated “#” in Formula IIa. The class ofpolymeric materials generated from monomers of this type producespolymeric hole transport films with a random distribution of AA, BB, andAB segments throughout the polymer. This can result in differentialdegrees of non-associative packing that ultimately determines theassociated film-forming properties. In some embodiments, thedistribution of monomeric segments can be manipulated so as to optimizeproperties of polymers made from monomers having Formula IIa for use inelectronic devices. In some embodiments, the monomer having Formula IIais deuterated. The term “deuterated” is intended to mean that at leastone H has been replaced by deuterium (“D”). The term “deuterated analog”refers to a structural analog of a compound or group in which one ormore available hydrogens have been replaced with deuterium. In adeuterated compound or deuterated analog, the deuterium is present in atleast 100 times the natural abundance level. In some embodiments, thecompound is at least 10% deuterated. By “% deuterated” or “%deuteration” is meant the ratio of deuterons to the sum of protons plusdeuterons, expressed as a percentage. In some embodiments, the monomeris at least 10% deuterated; in some embodiments, at least 20%deuterated; in some embodiments, at least 30% deuterated; in someembodiments, at least 40% deuterated; in some embodiments, at least 50%deuterated; in some embodiments, at least 60% deuterated; in someembodiments, at least 70% deuterated; in some embodiments, at least 80%deuterated; in some embodiments, at least 90% deuterated; in someembodiments, 100% deuterated.

Deuterated materials can be less susceptible to degradation by holes,electrons, excitons, or a combination thereof. Deuteration canpotentially inhibit degradation of the compound during device operation,which in turn can lead to improved device lifetime. In general, thisimprovement is accomplished without sacrificing other device properties.Furthermore, the deuterated compounds frequently have greater airtolerance than the non-deuterated analogs. This can result in greaterprocessing tolerance both for the preparation and purification of thematerials and in the formation of electronic devices using thematerials.

All of the above embodiments for Ar¹-Ar⁴ regarding the hole transportpolymer having Formula II apply equally well to Ar¹-Ar⁴ in the monomerhaving Formula IIa.

All of the above embodiments for R¹ regarding the hole transport polymerhaving Formula II apply equally well to R¹ in the monomer having FormulaIIa.

All of the above embodiments for b regarding the hole transport polymerhaving Formula II apply equally well to b in the monomer having FormulaIIa.

All of the above embodiments for R² regarding the hole transport polymerhaving Formula II apply equally well to R² in the monomer having FormulaIIa.

Any of the above embodiments for Formula IIa can be combined with one ormore of the other embodiments, so long as they are not mutuallyexclusive. For example, the embodiment in which Ar¹═Ar⁴ can be combinedwith the embodiment in which R¹=D. The same is true for the othernon-mutually-exclusive embodiments discussed above. The skilled personwould understand which embodiments were mutually exclusive and wouldthus readily be able to determine the combinations of embodiments thatare contemplated by the present application.

Some non-limiting examples of compounds having Formula IIa are shownbelow.

2e. Hole Transport Copolymer Having Formula III

The hole transport copolymer described herein has Formula III

wherein:

-   -   A is a monomeric unit having Formula la or Formula IIa;    -   B is a monomeric unit having at least three points of attachment        in the copolymer;    -   C is an aromatic monomeric unit or a deuterated analog thereof;    -   E is the same or different at each occurrence and is selected        from the group consisting of H, D, halide, alkyl, aryl,        arylamino, siloxane, ester, crosslinkable groups, deuterated        alkyl, deuterated aryl, deuterated arylamino, deuterated        siloxane, deuterated ester, and deuterated crosslinkable groups;    -   X, y, and z are the same or different and are mole fractions,        such that x+y+z=1, and x and y are non-zero.

Any of the “A”, “B”, or “C” monomeric units may have substituentsselected from the group consisting of D, F, CN, alkyl, fluoroalkyl,aryl, heteroaryl, amino, silyl, alkoxy, aryloxy, fluoroalkoxy, siloxane,siloxy, crosslinking groups, deuterated alkyl, deuteratedpartially-fluorinated alkyl, deuterated aryl, deuterated heteroaryl,deuterated amino, deuterated silyl, deuterated alkoxy, deuteratedaryloxy, deuterated fluoroalkoxy, deuterated siloxane, deuteratedsiloxy, and deuterated crosslinking groups.

In some embodiments of Formula III, the “A”, “B”, and “C” units areordered in a regular alternating pattern.

In some embodiments of Formula III, the “A”, “B”, and optional “C” unitsare ordered in blocks of like monomers.

In some embodiments of Formula III, the “A”, “B”, and optional “C” unitsare randomly arranged.

In some embodiments, the distribution of monomeric segments can bemanipulated so as to optimize properties of compounds having

Formula III for use in electronic devices. In some embodiments, thedifferent distribution can result in differential degrees ofnon-associative packing that ultimately determines the associatedfilm-forming properties.

In some embodiments, the copolymer having Formula III is deuterated. Theterm “deuterated” is intended to mean that at least one H has beenreplaced by deuterium (“D”). The term “deuterated analog” refers to astructural analog of a compound or group in which one or more availablehydrogens have been replaced with deuterium. In a deuterated copolymeror deuterated analog, the deuterium is present in at least 100 times thenatural abundance level. In some embodiments, the copolymer is at least10% deuterated. By “% deuterated” or “% deuteration” is meant the ratioof deuterons to the sum of protons plus deuterons, expressed as apercentage. In some embodiments, the copolymer is at least 10%deuterated; in some embodiments, at least 20% deuterated; in someembodiments, at least 30% deuterated; in some embodiments, at least 40%deuterated; in some embodiments, at least 50% deuterated; in someembodiments, at least 60% deuterated; in some embodiments, at least 70%deuterated; in some embodiments, at least 80% deuterated; in someembodiments, at least 90% deuterated; in some embodiments, 100%deuterated.

The deuteration can be present on one or more of monomeric units A, B,and C. The deuteration can be present on the copolymer backbone, onpendant groups, or both.

In some embodiments of Formula III, the copolymer has a M_(n)>10,000. Insome embodiments, the copolymer has a M_(n)>20,000; in some embodiments,M_(n)>50,000; in some embodiments, M_(n)>100,000; in some embodiments,M_(n)>150,000.

In some embodiments, Monomeric unit A has Formula la as described insection 2b above with all of the associated embodiments thereinidentified.

In some embodiments, Monomeric unit A has Formula IIa as described insection 2d above with all of the associated embodiments thereinidentified.

Monomeric unit B is a branching monomeric unit having at least threepoints of attachment in the copolymer.

In some embodiments, monomeric unit B is aromatic.

In some embodiments, monomeric unit B is aromatic with alkyl branchinggroups.

In some embodiments, monomeric unit B is aromatic with aromaticbranching groups.

In some embodiments, monomeric unit B is a triarylamine group.

In some embodiments, monomeric unit B has Formula VI

wherein:

-   -   Z is selected from the group consisting of C, Si, Ge, N, a        cyclic aliphatic moiety, an aromatic moiety, a deuterated cyclic        aliphatic moiety, or a deuterated aromatic moiety having at        least three bonding positions;    -   Y is a single bond, an alkyl, an aromatic moiety, a deuterated        alkyl, or a deuterated aromatic moiety, provided that when Y is        a single bond, alkyl, or deuterated alkyl, A is an aromatic or        deuterated aromatic moiety;    -   p is an integer from 3 to the maximum number of bonding        positions available on Ar; and    -   * represents a point of attachment in the copolymer.

In some embodiments, monomeric unit B has one of Formula VII, FormulaVIII, Formula IX, and Formula X

wherein:

-   -   Ar⁵ is an aromatic moiety or a deuterated aromatic moiety having        at least three bonding positions;    -   R⁶ is independently the same or different at each occurrence and        is selected from the group consisting of D, F, alkyl, aryl,        alkoxy, ester, aryloxy, silyl, a crosslinking group, deuterated        alkyl, deuterated aryl, deuterated alkoxy, deuterated ester,        deuterated aryloxy, deuterated silyl, and a deuterated        crosslinking group, wherein adjacent R⁶ groups can be joined        together to form a fused 5- or 6-membered aromatic ring;    -   k is the same or different at each occurrence and is an integer        from 0 to 4;    -   * represents a point of attachment in the copolymer.

In some embodiments of Formula VI Z is is an aromatic moiety derivedfrom a compound selected from benzene, naphthalene, anthracene,phenanthrene, substituted derivatives thereof, and deuterated analogsthereof.

Some non-limiting examples of monomeric unit B are shown below.

Monomeric unit C is an optional monomeric unit that is aromatic.

In some embodiments, C has one of the formulae given below.

In M1 through M19:

-   -   R¹² is the same or different at each occurrence and is selected        from the group consisting of D, alkyl, silyl, aryl, deuterated        alkyl, deuterated silyl, and deuterated aryl;    -   R¹³ is the same or different at each occurrence and is selected        from the group consisting of H, D, alkyl, and deuterated alkyl;    -   R¹⁴ is the same or different at each occurrence and is selected        from the group consisting of alkyl, aryl, and deuterated analogs        thereof;    -   R¹⁵ is the same or different at each occurrence and is selected        from the group consisting of aryl and deuterated aryl;    -   f is the same or different at each occurrence and is an integer        from 0 to the maximum number of positions available for        substituents;    -   g is an integer of 0-20; and    -   ** represents the point of attachment in the copolymer.

In some embodiments of M1 through M19, f is 0-2.

Some non-limiting examples of optional monomeric unit C are shown below.

Unit E is an end-capping unit for the copolymer.

In some embodiments of Formula III, E is a crosslinking group ordeuterated crosslinking group.

In some embodiments of Formula III, E is selected from aryl, ester,arylamino, crosslinkable groups, and deuterated analogs thereof.

In some embodiments of Formula III, E is selected from phenyl, biphenyl,diphenylamino, and deuterated analogs thereof.

In some embodiments of Formula III, E is H or D.

Some non-limiting examples of E are shown below.

In some embodiments of Formula III, x≧0.50.

In some embodiments of Formula III, y≧0.05; in some embodiments b≧0.10.

In some embodiments of Formula III, z=0.

In some embodiments of Formula III, z=0.01-0.05.

In some embodiments of Formula I, the molar ratio of A+B to E is in therange of 50:50 to 90:10; in some embodiments, 60:40 to 80:20.

Any of the above embodiments for Formula III can be combined with one ormore of the other embodiments, so long as they are not mutuallyexclusive. The skilled person would understand which embodiments weremutually exclusive and would thus readily be able to determine thecombinations of embodiments that are contemplated by the presentapplication.

Some non-limiting examples of compounds having Formula III are shownbelow.

In copolymer HIII-1, the end-capping unit E is a crosslinking group. Inone embodiment, the ratio of x:y:e=58:12:30.

In copolymer HIII-2, the end-capping unit E is a crosslinking group. Inone embodiment, the ratio of x:y:e=65:15:20.

The new monomers, polymers and copolymers can be made using anytechnique that will yield a C-C or C—N bond. A variety of suchtechniques are known, such as Suzuki, Yamamoto, Stille, and Pd— or Ni—catalyzed C—N couplings. Deuterated compounds can be prepared in asimilar manner using deuterated precursor materials or, more generally,by treating the non-deuterated compound with deuterated solvent, such asd6-benzene, in the presence of a Lewis acid H/D exchange catalyst, suchas aluminum trichloride or ethyl aluminum dichloride. Exemplarypreparations are given in the Examples.

The compounds can be formed into layers using solution processingtechniques. The term “layer” is used interchangeably with the term“film” and refers to a coating covering a desired area. The term is notlimited by size. The area can be as large as an entire device or assmall as a specific functional area such as the actual visual display,or as small as a single sub-pixel. Layers and films can be formed by anyconventional deposition technique, including vapor deposition, liquiddeposition (continuous and discontinuous techniques), and thermaltransfer. Continuous deposition techniques, include but are not limitedto, spin coating, gravure coating, curtain coating, dip coating,slot-die coating, spray coating, and continuous nozzle coating.Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

The new compounds having Formula I, Formula II, and Formula III can beused as hole transport materials and as hosts for electroluminescentmaterials. The new compounds also have utility in one or more layersbetween the hole injection layer and the hole transport layer.

3. Electronic Devices

Organic electronic devices that may benefit from having one or morelayers including at least one compound as described herein include, butare not limited to, (1) devices that convert electrical energy intoradiation (e.g., a light-emitting diode, light emitting diode display,lighting device, luminaire, or diode laser), (2) devices that detectsignals through electronics processes (e.g., photodetectors,photoconductive cells, photoresistors, photoswitches, phototransistors,phototubes, IR detectors, biosensors), (3) devices that convertradiation into electrical energy, (e.g., a photovoltaic device or solarcell), (4) devices that convert light of one wavelength to light of alonger wavelength, (e.g., a down-converting phosphor device); and (5)devices that include one or more electronic components that include oneor more organic semi-conductor layers (e.g., a transistor or diode).Other uses for the compositions according to the present inventioninclude coating materials for memory storage devices, antistatic films,biosensors, electrochromic devices, solid electrolyte capacitors, energystorage devices such as a rechargeable battery, and electromagneticshielding applications.

One illustration of an organic electronic device structure is shown inFIG. 1. The device 100 has a first electrical contact layer, an anodelayer 110 and a second electrical contact layer, a cathode layer 160,and a photoactive layer 140 between them. Additional layers mayoptionally be present. Adjacent to the anode may be a hole injectionlayer 120, sometimes referred to as a buffer layer. Adjacent to the holeinjection layer may be a hole transport layer 130, including holetransport material. Adjacent to the cathode may be an electron transportlayer 150, including an electron transport material. As an option,devices may use one or more additional hole injection or hole transportlayers (not shown) next to the anode 110 and/or one or more additionalelectron injection or electron transport layers (not shown) next to thecathode 160. Layers 120 through 150 are individually and collectivelyreferred to as the organic active layers.

In some embodiments, in order to achieve full color, the light-emittinglayer is pixellated, with subpixel units for each of the differentcolors. An illustration of a pixellated device is shown in FIG. 2. Thedevice 200 has anode 110, hole injection layer 120, hole transport layer130, electroluminescent layer 140, electron transport layer 150, andcathode 160. The electroluminescent layer is divided into subpixels 141,142, 143, which are repeated across the layer. In some embodiments, thesubpixels represent red, blue and green color emission. Although threedifferent subpixel units are depicted in FIG. 2, two or more than threesubpixel units may be used.

The different layers will be discussed further herein with reference toFIG. 1. However, the discussion applies to FIG. 2 and otherconfigurations as well.

In some embodiments, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in some embodiments, 1000-2000 Å;hole injection layer 120, 50-2000 Å, in some embodiments, 200-1000 Å;hole transport layer 130, 50-3000 Å, in some embodiments, 200-2000 Å;photoactive layer 140, 10-2000 Å, in some embodiments, 100-1000 Å;electron transport layer 150, 50-2000 Å, in some embodiments, 100-1000Å; cathode 160, 200-10000 Å, in some embodiments, 300-5000 Å. Thedesired ratio of layer thicknesses will depend on the exact nature ofthe materials used.

One or more of the new compounds having Formula I described herein maybe present in one or more of the electroactive layers of a device. Insome embodiments, the new compounds are useful as hole transportmaterials in layer 130. In some embodiments, the new compounds areuseful as host materials for photoactive dopant materials in photoactivelayer 140. The term “dopant” is intended to mean a material, within alayer including a host material, that changes the electroniccharacteristic(s) or the targeted wavelength(s) of radiation emission,reception, or filtering of the layer compared to the electroniccharacteristic(s) or the wavelength(s) of radiation emission, reception,or filtering of the layer in the absence of such material. The term“host material” is intended to mean a material to which a dopant isadded. The host material may or may not have electroniccharacteristic(s) or the ability to emit, receive, or filter radiation.In some embodiments, the host material is present in higherconcentration.

In some embodiments, an organic electronic device includes an anode, acathode, and at least one organic active layer therebetween, where theorganic active layer includes a compound of Formula I.

In some embodiments, an organic electronic device includes an anode, acathode, and a photoactive layer therebetween, and further includes anadditional organic active layer including a compound of Formula I. Insome embodiments, the additional organic active layer is a holetransport layer.

The anode 110 is an electrode that is particularly efficient forinjecting positive charge carriers. It can be made of, for examplematerials containing a metal, mixed metal, alloy, metal oxide ormixed-metal oxide, or it can be a conducting polymer, and mixturesthereof. Suitable metals include the Group 11 metals, the metals inGroups 4, 5, and 6, and the Group 8-10 transition metals. If the anodeis to be light-transmitting, mixed-metal oxides of Groups 12, 13 and 14metals, such as indium-tin-oxide, are generally used. The anode may alsoinclude an organic material such as polyaniline as described in“Flexible light-emitting diodes made from soluble conducting polymer,”Nature vol. 357, pp 477 479 (11 Jun. 1992). At least one of the anodeand cathode should be at least partially transparent to allow thegenerated light to be observed.

Optional hole injection layer 120 includes hole injection materials. Theterm “hole injection layer” or “hole injection material” is intended tomean electrically conductive or semiconductive materials and may haveone or more functions in an organic electronic device, including but notlimited to, planarization of the underlying layer, charge transportand/or charge injection properties, scavenging of impurities such asoxygen or metal ions, and other aspects to facilitate or to improve theperformance of the organic electronic device. Hole injection materialsmay be polymers, oligomers, or small molecules, and may be in the formof solutions, dispersions, suspensions, emulsions, colloidal mixtures,or other compositions.

The hole injection layer can be formed with polymeric materials, such aspolyaniline (PAN I) or polyethylenedioxythiophene (PEDOT), which areoften doped with protonic acids. The protonic acids can be, for example,poly(styrenesulfonic acid), poly(2-acrylamido-2-methyl-1-propanesulfonicacid), and the like. The hole injection layer 120 can include chargetransfer compounds, and the like, such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In someembodiments, the hole injection layer 120 is made from a dispersion of aconducting polymer and a colloid-forming polymeric acid. Such materialshave been described in, for example, published U.S. patent applications2004-0102577, 2004-0127637, and 2005-0205860.

Layer 130 includes hole transport material. In some embodiments, thehole transport layer includes a compound having Formula I.

In some embodiments, the hole transport layer includes only a compoundhaving Formula I, where additional materials that would materially alterthe principle of operation or the distinguishing characteristics of thelayer are not present therein.

In some embodiments, layer 130 includes other hole transport materials.Examples of hole transport materials for the hole transport layer havebeen summarized for example, in Kirk-Othmer Encyclopedia of ChemicalTechnology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Bothhole transporting small molecules and polymers can be used. Commonlyused hole transporting molecules include, but are not limited to:4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA);N,N′-diphenyl-N,N′-bis(3-methylphenyl)[1,1′-biphenyl]-4,4′-diamine(TPD); 4,4′-bis(carbazol-9-yl)biphenyl (CBP);1,3-bis(carbazol-9-yl)benzene (mCP); 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC);N,N′-bis(4-methylphenyl)-N,N′bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane(DCZB); N,N,N′,N′-tetrakis(4-methylphenyI)-(1,1′-biphenyl)-4,4′-diamine(TTB); N,N′-bis(naphthalen-1-yl)—N,N′-bis-(phenyl)benzidine (α-NPB); andporphyrinic compounds, such as copper phthalocyanine.

Commonly used hole transporting polymers include, but are not limitedto, polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules such asthose mentioned above into polymers such as polystyrene andpolycarbonate. In some cases, the polymers and copolymers arecrosslinkable. Examples of crosslinkable hole transport polymers can befound in, for example, published US patent application 2005-0184287 andpublished PCT application WO 2005/052027. In some embodiments, the holetransport layer is doped with a p-dopant, such astetrafluoro-tetracyanoquinodimethane andperylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride.

Depending upon the application of the device, the photoactive layer 140can be a light-emitting layer that is activated by an applied voltage(such as in a light-emitting diode or light-emitting electrochemicalcell), a layer of material that absorbs light and emits light having alonger wavelength (such as in a down-converting phosphor device), or alayer of material that responds to radiant energy and generates a signalwith or without an applied bias voltage (such as in a photodetector orphotovoltaic device).

In some embodiments, the photoactive layer includes an organicelectroluminescent (“EL”) material. Any EL material can be used in thedevices, including, but not limited to, small molecule organicfluorescent compounds, fluorescent and phosphorescent metal complexes,conjugated polymers, and mixtures thereof. Examples of fluorescentcompounds include, but are not limited to, chrysenes, pyrenes,perylenes, rubrenes, coumarins, anthracenes, thiadiazoles, derivativesthereof, and mixtures thereof. Examples of metal complexes include, butare not limited to, metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium andplatinum electroluminescent compounds, such as complexes of iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., U.S. Pat. No. 6,670,645 and Published PCTApplications WO 03/063555 and WO 2004/016710, and organometalliccomplexes described in, for example, Published PCT Applications WO03/008424, WO 03/091688, and WO 03/040257, and mixtures thereof. In somecases the small molecule fluorescent or organometallic materials aredeposited as a dopant with a host material to improve processing and/orelectronic properties. Examples of conjugated polymers include, but arenot limited to poly(phenylenevinylenes), polyfluorenes,poly(spirobifluorenes), polythiophenes, poly(p-phenylenes), copolymersthereof, and mixtures thereof.

In some embodiments, the photoactive layer 140 includes anelectroluminescent material in a host material having Formula I. In someembodiments, a second host material is also present. In someembodiments, photoactive layer 140 includes only an electroluminescentmaterial and a host material having Formula I. In some embodiments,photoactive layer 140 includes only an electroluminescent material, afirst host material having Formula I, and a second host material.Examples of second host materials include, but are not limited to,chrysenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes,anthracenes, quinolines, isoquinolines, quinoxalines, phenylpyridines,benzodifurans, and metal quinolinate complexes.

Optional layer 150 can function both to facilitate electron transport,and also serve as a hole injection layer or confinement layer to preventquenching of the exciton at layer interfaces. Preferably, this layerpromotes electron mobility and reduces exciton quenching. Examples ofelectron transport materials which can be used in the optional electrontransport layer 150, include metal chelated oxinoid compounds, includingmetal quinolate derivatives such as tris(8-hydroxyquinolato)aluminum(AlQ), bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ); and azole compounds suchas 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthrolines such as4,7-diphenyl-1,10-phenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); triazines;fullerenes; and mixtures thereof.

In some embodiments, the electron transport material is selected fromthe group consisting of metal quinolates and phenanthroline derivatives.In some embodiments, the electron transport layer further includes ann-dopant. N-dopant materials are well known. The n-dopants include, butare not limited to, Group 1 and 2 metals; Group 1 and 2 metal salts,such as LiF, CsF, and Cs₂CO₃; Group 1 and 2 metal organic compounds,such as Li quinolate; and molecular n-dopants, such as leuco dyes, metalcomplexes, such as W₂(hpp)₄ wherehpp=1,3,4,6,7,8-hexahydro-2H-pyrimido-[1,2-a]-pyrimidine andcobaltocene, tetrathianaphthacene,bis(ethylenedithio)tetrathiafulvalene, heterocyclic radicals ordiradicals, and the dimers, oligomers, polymers, dispiro compounds andpolycycles of heterocyclic radical or diradicals.

An optional electron injection layer may be deposited over the electrontransport layer. Examples of electron injection materials include, butare not limited to, Li-containing organometallic compounds, LiF, Li₂O,Li quinolate, Cs-containing organometallic compounds, CsF, Cs₂O, andCs₂CO₃. This layer may react with the underlying electron transportlayer, the overlying cathode, or both. When an electron injection layeris present, the amount of material deposited is generally in the rangeof 1-100 Å, in some embodiments 1-10 Å.

The cathode 160, is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode can be anymetal or nonmetal having a lower work function than the anode. Materialsfor the cathode can be selected from alkali metals of Group 1 (e.g., Li,Cs), the Group 2 (alkaline earth) metals, the Group 12 metals, includingthe rare earth elements and lanthanides, and the actinides. Materialssuch as aluminum, indium, calcium, barium, samarium and magnesium, aswell as combinations, can be used.

It is known to have other layers in organic electronic devices. Forexample, there can be a layer (not shown) between the anode 110 and holeinjection layer 120 to control the amount of positive charge injectedand/or to provide band-gap matching of the layers, or to function as aprotective layer. Layers that are known in the art can be used, such ascopper phthalocyanine, silicon oxy-nitride, fluorocarbons, silanes, oran ultra-thin layer of a metal, such as Pt. Alternatively, some or allof anode layer 110, active layers 120, 130, 140, and 150, or cathodelayer 160, can be surface-treated to increase charge carrier transportefficiency. The choice of materials for each of the component layers ispreferably determined by balancing the positive and negative charges inthe emitter layer to provide a device with high electroluminescenceefficiency.

It is understood that each functional layer can be made up of more thanone layer.

The device layers can be formed by any deposition technique, orcombinations of techniques, including vapor deposition, liquiddeposition, and thermal transfer. Substrates such as glass, plastics,and metals can be used. Substrates can be flexible or non-flexible.Conventional vapor deposition techniques can be used, such as thermalevaporation, chemical vapor deposition, and the like. The organic layerscan be applied from solutions or dispersions in suitable solvents, usingconventional coating or printing techniques, including but not limitedto spin-coating, dip-coating, roll-to-roll techniques, ink-jet printing,continuous nozzle printing, screen-printing, gravure printing and thelike.

For liquid deposition methods, a suitable solvent for a particularcompound or related class of compounds can be readily determined by oneskilled in the art. For some applications, it is desirable that thecompounds be dissolved in non-aqueous solvents. Such non-aqueoussolvents can be relatively polar, such as C₁ to C₂₀ alcohols, ethers,and acid esters, or can be relatively non-polar such as C₁ to C₁₂alkanes or aromatics such as toluene, xylenes, trifluorotoluene and thelike. Other suitable liquids for use in making the liquid composition,either as a solution or dispersion as described herein, including thenew compounds, includes, but not limited to, chlorinated hydrocarbons(such as methylene chloride, chloroform, chlorobenzene), aromatichydrocarbons (such as substituted and non-substituted toluenes andxylenes), including triflurotoluene), polar solvents (such astetrahydrofuran (THP), N-methyl pyrrolidone) esters (such asethylacetate) alcohols (isopropanol), ketones (cyclopentatone) andmixtures thereof. Suitable solvents for electroluminescent materialshave been described in, for example, published PCT application WO2007/145979.

In some embodiments, the device is fabricated by liquid deposition ofthe hole injection layer, the hole transport layer, and the photoactivelayer, and by vapor deposition of the anode, the electron transportlayer, an electron injection layer and the cathode.

It is understood that the efficiency of devices made with the newcompositions described herein, can be further improved by optimizing theother layers in the device. For example, more efficient cathodes such asCa, Ba or LiF can be used. Shaped substrates and novel hole transportmaterials that result in a reduction in operating voltage or increasequantum efficiency are also applicable. Additional layers can also beadded to tailor the energy levels of the various layers and facilitateelectroluminescence.

In some embodiments, the device has the following structure, in order:anode, hole injection layer, hole transport layer, photoactive layer,electron transport layer, electron injection layer, cathode.

Although methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described below. In addition, thematerials, methods, and examples are illustrative only and not intendedto be limiting. All publications, patent applications, patents, andother references mentioned herein are incorporated by reference in theirentirety.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Synthesis Example 1

This example illustrates the synthesis of polymer H1.

Synthesis of Compound H1 a:

To a three neck 1L flask was added 1-bromo-2,5-dihexyl-4-iodobenzene(4.00 g, 8.86 mmmol),3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (2.73 g,9.31 mmol), sodium carbonate (2.,82 g, 26 mmol), and 50 mL ofo-xylene:water (1:1). The solution was degassed by bubbling nitrogenthrough it for 15 minutes.

Tetrakis(triphenylphosphine)Pd(0) (0.41 g, 0.355 mmol) was added and thesolution was further degassed for 5 min. The reaction was heated to 120°C. for 24 hrs. Once the reaction was cooled to room temperature theorganic and aqueous portions of the reaction mixture were separated andthe organic was concentrated and purified using silica chromatography(hexane). The product was isolated in 51% yield.

Synthesis of Compound H1b:

To a three neck 1L flask was added H1a (2.2 g, 4.49 mmmol),4-chlorophenylboronic acid (0.771 g, 9.31 mmol), cesium carbonate (3.65g, 11.2 mmol), 60 mL DEM, 30 mL EtOH and 10mL of water. The resultingsolution was degassed by bubbling nitrogen through it for 15 minutes.Pd(dppf)C12 (0.11 g, 0.224 mmol) was added and the solution was furtherdegassed for 5 min. The reaction was heated to 65° C. overnight. Oncethe reaction was cooled to room temperature, the organic and aqueousportions of the reaction mixture were separated and the organic portionwas concentrated and purified using silica chromatography (hexane). Theproduct was isolated in 68% yield.

Synthesis of compound H1c:

Under a nitrogen atmosphere a 200 mL round bottom was loaded with H1b(1.50 g, 2.87 mmol), propylbiphenylamine (0.667 g, 3.16 mmol), Pd2(dba)3(0.132 g, 0.144 mmol), tri-tbutyl phosphine (0.058 g, 0.287 mmol) andtoluene (30 mL). The mixture was stirred and sodium t-butoxide (0.304,2.87 mmol) was added. The reaction was heated to 97° C. for 16 hours.The reaction was cooled to room temperature; water (100 mL) and toluene(100 mL) were added. The aqueous layer was separated and back extractedwith an addition 100 mL of toluene. The organic layer was dried withsodium sulfate and concentrated on Celite for purification. The solutionwas purified via silicachromatography (dichloro-methane:hexane 0-30%)and the fractions of product were concentrated to give the desiredproduct as a white crystalline solid in 46% yield.

Synthesis of Compound H1d:

To a 200 mL round bottom, in the glove box, was added compound H1c(0.900 g, 1.29 mmol), 4-bromo-4′iodobiphenyl (1.39 g, 3.87 mmol),Pd2(dba)3 (0.095 g, 0.10 mmol), dppf (0.115 g, 0.21 mmol) and toluene(20 mL). The mixture was stirred and sodium t-butoxide (0.372, 3.87mmol) was added. The reaction was heated to 100° C. After 22 hoursconversion to the desired product was complete. The reaction was cooledto room temperature; water (100 mL) and toluene (100 mL) were added. Theaqueous layer was separated and back extracted with an addition 100 mLof toluene. The organic layer was dried with sodium sulfate andconcentrated on Celite for purification. Purification was performed viaflash chromatography (0-10% Hex:DCM). Once the product was isolated itwas washed with EtOH to yield a white solid which was filtered. Thesolid was dried to produce a white crystalline solid (0.700 g, 47%yield).

Synthesis of H1:

Compound H1d (0.561 mmol) and 4-bromobiphenyl (0.036 mmol) were added toa scintillation vial and dissolved in 15 mL toluene. A clean, dry 50 mLSchlenk tube was charged with bis(1,5-cyclooctadiene)nickel(0) (1.21mmol). 2,2′-Dipyridyl (1.21 mmol) and 1,5-cyclooctadiene (1.21 mmol)were weighed into a scintillation vial and dissolved in 4.0 mLN,N′-dimethylformamide. The solution was added to the Schlenk tube,which was then inserted into an aluminum block and heated to an internaltemperature of 60° C. The catalyst system was held at 60° C. for 30minutes. The monomer solution in toluene was added to the Schlenk tubeand the tube was sealed. The polymerization mixture was stirred at 60°C. for three hours. The Schlenk tube was then removed from the block andallowed to cool to room temperature. The contents were poured intoHCl/methanol (5% v/v, conc. HCI). After stirring for 45 minutes, thepolymer was collected by vacuum filtration and dried under high vacuum.The polymer was dissolved in toluene (1% wt/v) and passed through acolumn containing aluminum oxide, basic. (6 gram) layered onto silicagel (6 gram). The polymer/toluene filtrate was concentrated (2.5% wt/vtoluene) and triturated with 3-pentanone. The toluene/3-pentanonesolution was decanted from the semi-solid polymer which was thendissolved with 15 mL toluene before being poured into stirring methanolto yield compound H1 in 50% yield. GPC analysis with polystyrenestandards Mn=76,133; Mw=134,698; PDI=1.8.

Synthesis Example 2

This example illustrates the synthesis of polymer H2.

Synthesis of compound H2a:

To a three neck 1L flask was added 1-bromo-2,5-dihexyl-4-iodobenzene(3.00 g, 6.65 mmmol), 4-chloro-2-methylphenylboronic acid (1.07 g, 6.26mmol), sodium carbonate (1.68 g, 26.59 mmol), and 50 mL ofo-xylene:water (1:1). The solution was degassed by bubbling nitrogenthrough it for 15 minutes. Tetrakis(triphenylphosphine)Pd(0) (0.38 g,0.332 mmol) was added, and the solution was further degassed for 5 min.The reaction was heated to 120° C. for 16 hrs. Once the reaction wascooled to room temperature, the organic and aqueous portions of thereaction mixture were separated and the organic portion was concentratedand purified using silica chromatography (hexane). The product wasisolated in 48% yield.

Synthesis of compound H2b:

To a three neck 1L flask was added compound H2a (2.600 g, 5.78 mmol),3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (1.78 g,6.07 mmol), sodium carbonate (1.84 g, 17.34 mmol), and 200 mL ofm-xylene:water (1:1). The resulting solution was degassed by bubblingnitrogen through it for 15 minutes.

Tetrakis(triphenylphosphine)Pd(0) (0.267 g, 0.231 mmol) was added andthe solution was further degassed for 5 min. The reaction was thenstirred and heated to 100° C. for 28 hrs. The resulting material wasisolated by adding 100 mL of toluene and 50 mL of H2O. The organic layerwas separated and the aqueous layer was back extracted with anadditional 100 mL of water. The organic layer was dried with sodiumsulfate, filtered through a pad of Celite and concentrated to give 4 gof crude solid. The material was purified using silica anddicholoromethane:hexane-0-30% in as a clear oil in 44% yield.

Synthesis of compound H2c:

Under a nitrogen atmosphere, a 200 mL round bottom flask was loaded withH2b (1.375 g, 2.56 mmol), propylbiphenylamine (0.596 g, 2.82 mmol),Pd2(dba)3 (0.117 g, 0.128 mmol), tri-tbutyl phosphine (0.0519 g, 0.256mmol), and toluene (30 mL). The mixture was stirred and sodiumt-butoxide (0.271, 2.82 mmol) was added. The reaction mixture was heatedto 97° C. for 16 hours. The reaction mixture was then cooled to roomtemperature; water (100 mL) and toluene (100 mL) were added. The aqueouslayer was separated and back extracted with an addition 100 mL oftoluene. The organic layer was dried with sodium sulfate andconcentrated on Celite for purification. The solution was purified viasilica chromatography (dichloromethane:hexane 0-30%) and the fractionsof product were concentrated to give the desired product as a whitecrystalline solid in 39% yield.

Synthesis of compound H2d:

To a 200 mL round bottom, in the glove box, was added compound H2c(0.700 g, 0.984 mmol), 4-bromo-4′iodobiphenyl (1.06 g, 2.95 mmol),Pd2(dba)3 (0.072 g, 0.079 mmol), dppf (0.087 g, 0.158 mmol), and toluene(20 mL). The mixture was stirred and sodium t-butoxide (0.284, 2.95mmol) was added. The reaction was heated to 100° C. After 22 hoursconversion to the desired product was complete. The reaction was cooledto room temperature; water (100 mL) and toluene (100 mL) were added. Theaqueous layer was separated and back extracted with an additional 100 mLof toluene. The organic layer was dried with sodium sulfate andconcentrated on Celite for purification. Purification was performed viaflash chromatography (0-10% Hex:DCM). Once the product was isolated itwas washed with EtOH to yield a white solid which was filtered. Thesolid was dried to give a white crystalline solid (0.743 g, 64.6%yield).

Synthesis of H2:

H2d (0.597 mmol) and 4-bromobiphenyl (0.038 mmol) were added to ascintillation vial and dissolved in 15 mL toluene. A clean, dry 50 mLSchlenk tube was charged with bis(1,5-cyclooctadiene)nickel(0) (1.28mmol), 2,2′-Dipyridyl (1.28 mmol), and 1,5-cyclooctadiene (1.28 mmol)were weighed into a scintillation vial and dissolved in 4.25 mLN,N′-dimethylformamide. The solution was added to the Schlenk tube,which was then inserted into an aluminum block and heated to an internaltemperature of 60° C. The catalyst system was held at 60° C. for 30minutes. The monomer solution in toluene was added to the Schlenk tubeand the tube was sealed. The polymerization mixture was stirred at 60°C. for three hours. The Schlenk tube was then removed from the block andallowed to cool to room temperature. The contents were poured intoHCl/methanol (5% v/v, conc. HCl). After stirring for 45 minutes, thepolymer was collected by vacuum filtration and dried under high vacuum.The polymer was dissolved in toluene (1% wt/v) and passed through acolumn containing aluminum oxide, basic (6 gram) layered onto silica gel(6 gram). The polymer/toluene filtrate was concentrated (2.5% wt/vtoluene) and triturated with 3-pentanone. The toluene/3-pentanonesolution was decanted from the semi-solid polymer which was thendissolved with 16 mL toluene before being poured into stirring methanolto yield compound H2 in 59% yield. GPC analysis with polystyrenestandards Mn=80,612; Mw =128,801; PDI=1.6.

Synthesis Example 3

This example illustrates the synthesis of polymer H12.

Synthesis of Monomer 12:

This monomer was synthesized as exemplified for H2c by replacing thepropylbiphenylamine with biphenyl-2-amine.

Synthesis of H12:

Polymer H12 was synthesized as described for H2 to obtain polymer H12 in50% yield. GPC analysis with polystyrene standards Mn =86,898; Mw=148,345; PDI =1.7.

DEVICE EXAMPLES (1) Materials

-   ET-1 is shown below.

-   ET-2 is an aryl phosphine oxide.-   ET-3 is lithium quinolate (LiQ).-   HIJ-1 is a hole injection material which is made from an aqueous    dispersion of an electrically conductive polymer and a polymeric    fluorinated sulfonic acid. Such materials have been described in,    for example, published U.S. patent applications US 2004/0102577, US    2004/0127637, and US 2005/0205860, and published PCT application WO    2009/018009.-   HTM-1 is a triarylamine polymer. The polymer can be made using known    C—C and C—N coupling techniques. Such materials have been described    in, for example, published PCT Application WO2011159872.-   Host H-1 is a deuterated diaryl anthracene. The compound can be made    using known C—C and C—N coupling techniques. Such materials have    been described in published PCT Application WO2011028216.-   D-1 is a blue benzofluorene dopant. Such materials have been    described, for example, in U.S. Pat. No. 8,465,848.-   D-2 is a blue benzofluorene dopant. Such materials have been    described, for example, in U.S. Pat. No. 8,465,848.-   Hole Transport Compounds are specified in the examples device    examples that follow.

(2) Device Fabrication

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 30 ohms/square and 80% light transmission. Thepatterned ITO substrates were cleaned ultrasonically in aqueousdetergent solution and rinsed with distilled water. The patterned ITOwas subsequently cleaned ultrasonically in acetone, rinsed withisopropanol, and dried in a stream of nitrogen.

Device Type 1: Immediately before device fabrication the cleaned,patterned ITO substrates were treated with UV ozone for 10 minutes.Immediately after cooling, an aqueous dispersion of hole injectionmaterial was spin-coated over the ITO surface and heated to removesolvent. After cooling, the substrates were then spin-coated with ananisole:toluene solution of hole transport material, and then heated toremove solvent. After cooling the substrates were spin-coated with amethyl benzoate solution of the host and dopant, and heated to removesolvent. The substrates were masked and placed in a vacuum chamber. Alayer of electron transport material was deposited by thermalevaporation, followed by a layer of electron injection material. Maskswere then changed in vacuo and a layer of Al was deposited by thermalevaporation. The chamber was vented, and the devices were encapsulatedusing a glass lid, dessicant, and UV curable epoxy.

Device Type 2: Immediately before device fabrication the cleaned,patterned ITO substrates were treated with UV ozone for 10 minutes.Immediately after cooling, an aqueous dispersion of hole injectionmaterial was spin-coated over the ITO surface and heated to removesolvent. After cooling, the substrates were then spin-coated with ananisole:toluene solution of hole transport material, and then heated toremove solvent. The workpieces were then placed in a vacuum chamber.Layers of the photoactive and host materials, electron transportmaterials, and the Al cathode were then deposited sequentially bythermal evaporation using the appropriate masks. The chamber was vented,and the devices were encapsulated using a glass lid, dessicant, and UVcurable epoxy.

(3) Device Characterization

The OLED samples were characterized by measuring their (1)current-voltage (I-V) curves, (2) electroluminescence radiance versusvoltage, and (3) electroluminescence spectra versus voltage. All threemeasurements were performed at the same time and controlled by acomputer. The current efficiency of the device at a certain voltage isdetermined by dividing the electroluminescence radiance of the LED bythe current density needed to run the device. The unit is a cd/A. Thepower efficiency is the current efficiency divided by the operatingvoltage. The unit is Im/W. The color coordinates were determined usingeither a

Minolta CS-100 meter or a Photoresearch PR-705 meter.

(4) Device Examples 1, 2 and Comparative Example A

These examples demonstrates the fabrication and performance of devicesincluding a hole transport polymer having Formula I. The devices weremade as described above for Device Type 1 and had the following layers:

-   -   Anode=ITO (50 nm)    -   HIL=HIJ-1 (100 nm)    -   HTL=see table (105 nm)    -   EML=7 wt % D-1 : 93 wt % H-1 (40 nm)    -   ETL=ET-1 (20 nm)    -   EIL=ET-3 (3 nm)    -   Cathode =Al (100 nm)

The results are given in Table 1 below.

TABLE 1 Device Results Hole Transport Voltage EQE C.E. Example Polymer(V) (%) (cd/A) CIE (x, y) 1 Compound H1 5.9 7.0 6.0 (0.14, 0.10) 2Compound H2 6.2 7.0 6.2 (0.14, 0.10) Comparative HTM-1 5.2 6.6 5.6(0.14, 0.10) A All data @ 1000 nits. Voltage measured at 15 mA/cm².E.Q.E. is the external quantum efficiency; CIE (x, y) are the x and ycolor coordinates according to the C.I.E. chromaticity scale (CommissionInternationale de L'Eclairage, 1931.

(5) Device Examples 3, 4 and Comparative Example B

These examples demonstrates the fabrication and performance of devicesincluding a hole transport polymer having Formula I. The devices weremade as described above for Device Type 1 and had the following layers:

-   -   Anode=ITO (50 nm)    -   HIL=HIJ-1 (100 nm)    -   HTL=see table (100 nm)    -   EML=7 wt % D-1 : 93 wt % H-1 (40 nm)    -   ETL=60 wt % ET-2 : 40 wt % ET-3 (20 nm)    -   EIL=ET-3 (3 nm)    -   Cathode=Al (100 nm) The results are given in Table 2 below.

TABLE 2 Device Results Hole Transport Voltage EQE C.E. CIE ExamplePolymer (V) (%) (cd/A) (x, y) 3 Compound H2 5.7 6.3 5.5 (0.14, 0.10) 4Compound H12 6.0 6.3 6.0 (0.14, 0.11) Comparative HTM-1 5.0 5.5 4.8(0.14, 0.10) B All data @ 1000 nits. Voltage measured at 15 mA/cm².E.Q.E. is the external quantum efficiency; CIE (x, y) are the x and ycolor coordinates according to the C.I.E. chromaticity scale (CommissionInternationale de L'Eclairage, 1931.

(6) Device Examples 5, 6 and Comparative Example C

These examples demonstrates the fabrication and performance of devicesincluding a hole transport polymer having Formula I. The devices weremade as described above for Device Type 2 and had the following layers:

-   -   Anode=ITO (50 nm)    -   HIL=HIJ-1 (100 nm)    -   HTL=see table (105 nm)    -   EML=20 wt % D-2 :80 wt % H-1 (33 nm)    -   ETL=ET-1 (20 nm)    -   EIL=ET-3 (3 nm)    -   Cathode=Al (100 nm)

The results are given in Table 3 below.

TABLE 3 Device Results Hole Transport Voltage EQE C.E. CIE ExamplePolymer (V) (%) (cd/A) (x, y) 5 Compound H1 4.7 9.6 8.4 (0.14, 0.10) 6Compound H2 5.1 9.9 8.8 (0.14, 0.10) Comparative HTM-1 4.2 8.9 8.0(0.14, 0.10) C All data @ 1000 nits. Voltage measured at 15 mA/cm².E.Q.E. is the external quantum efficiency; CIE (x, y) are the x and ycolor coordinates according to the C.I.E. chromaticity scale (CommissionInternationale de L'Eclairage, 1931.

(7) Device Example 7 and Comparative Example D

These examples demonstrates the fabrication and performance of devicesincluding a hole transport polymer having Formula I. The devices weremade as described above for Device Type 2 and had the following layers:

-   -   Anode=ITO (50 nm)    -   HIL=HIJ-1 (60 nm)    -   HTL=see table (20 nm)    -   EML=7 wt % D-2 : 93 wt % H-1 (20 nm)    -   ETL=60 wt % ET-2 : 40 wt % ET-3 (20 nm)    -   EIL=ET-3 (3 nm)    -   Cathode=Al (100 nm)

The results are given in Table 4 below.

TABLE 4 Device Results Hole Transport Voltage EQE C.E. Example Polymer(V) (%) (cd/A) CIE (x, y) 7 Compound H12 4.2 9.7 10.7 (0.14, 0.14)Comparative HTM-1 4.0 8.5 9.1 (0.14, 0.13) D All data @ 1000 nits.Voltage measured at 15 mA/cm². E.Q.E. is the external quantumefficiency; CIE (x, y) are the x and y color coordinates according tothe C.I.E. chromaticity scale (Commission Internationale de L'Eclairage,1931.

(8) Device Example 8, 9 and Comparative Example E

These examples demonstrates the fabrication and performance of devicesincluding a hole transport polymer having Formula I. The devices weremade as described above for Device Type 2 and had the following layers:

-   -   Anode=ITO (50 nm)    -   HIL=HIJ-1 (60 nm)    -   HTL=see table (19 nm)    -   EML=7 wt % D-2 : 93 wt % H-1 (20 nm)    -   ETL=60 wt % ET-2 : 40 wt % ET-3 (20 nm)    -   EIL=ET-3 (3.8 nm)    -   Cathode=Al (100 nm)

The results are given in Table 5 below.

TABLE 5 Device Results Hole Transport Voltage EQE C.E. Example Polymer(V) (%) (cd/A) CIE (x, y) 8 Compound H1 4.3 9.6 10.3 (0.138, 0.130) 9Compound H2 4.3 10.1 10.2 (0.139, 0.120) Comparative HTM-1 4.2 8.4 8.6(0.139, 0.121) E All data @ 1000 nits. Voltage measured at 15 mA/cm².E.Q.E. is the external quantum efficiency; CIE (x, y) are the x and ycolor coordinates according to the C.I.E. chromaticity scale (CommissionInternationale de L'Eclairage, 1931.

Described herein is a hole transport polymer having a carbazole groupand an amino nitrogen, wherein said polymer has Formula I.

In Formula I; Ar¹, Ar², and Ar⁴ are the same or different and aresubstituted or unsubstituted aryl groups or deuterated aryl groups, andAr³ is substituted or unsubstituted aryl groups or deuterated arylgroups. Further, E is the same or different at each occurrence and isselected from the group consisting of H, D, halide, alkyl, aryl,siloxane, ester, deuterated alkyl, deuterated aryl, deuterated siloxane,deuterated ester, and a crosslinking group. Also, R¹-R² are the same ordifferent at each occurrence and are selected from the group consistingof D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, alkoxy,ester, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl,deuterated partially-fluorinated alkyl, deuterated aryl, deuteratedheteroaryl, deuterated amino, deuterated silyl, deuterated alkoxy,deuterated ester, deuterated aryloxy, deuterated fluoroalkoxy,deuterated siloxane, deuterated siloxy, and crosslinking groups, whereinadjacent groups selected from R¹ and R² can be joined together to form afused ring. Finally; a is an integer from 0-4,b is an integer from 0-3,and n is an integer greater than or equal to1.

In some embodiments of Formula I, Ar¹-Ar⁴ are aryl groups having nofused rings. There are also embodiments of Formula I wherein one or bothof Ar¹ and Ar⁴ has Formula a:

Here; R⁹ is the same or different at each occurrence and is selectedfrom the group consisting of D, alkyl, alkoxy, siloxane ester, andsilyl, wherein adjacent R⁹ groups can be joined together to form a fusedring. Also; p is the same or different at each occurrence and is aninteger from 0-4, r is an integer from 1 to 5, and* indicates the pointof attachment to E.

In some embodiments of the hole transport with Formula I; Ar¹ and Ar⁴are selected from the group consisting of phenyl, biphenyl, terphenyl,deuterated analogs thereof, and derivatives thereof having one or moresubstituents selected from the group consisting of fluoro, alkyl,alkoxy, silyl, siloxy, a substituent with a crosslinking group, anddeuterated analogs thereof.

In some embodiments of the hole transport polymer with Formula I, Ar²has Formula a′

Here; R⁹ is the same or different at each occurrence and is selectedfrom the group consisting of D, alkyl, alkoxy, ester, siloxane, silyl,deuterated alkyl, deuterated alkoxy, deuterated siloxane, deuteratedsilyl, wherein adjacent R⁹ groups can be joined together to form a fusedring. Also; p is the same or different at each occurrence and is aninteger from 0-4, r is an integer from 1 to 5, * indicates the point ofattachment to the amino-nitrogen atom, and ** indicates the point ofattachment to the carbazole group.

In some embodiments of the hole transport polymer with Formula I; Ar² isselected from the group consisting of 1-naphthyl, 2-naphthyl,anthracenyl, fluorenyl, deuterated analogs thereof, and derivativesthereof having one or more substituents selected from the groupconsisting of fluoro, alkyl, alkoxy, silyl, siloxy, a substituent with acrosslinking group, and deuterated analogs thereof.

In some embodiments of the hole transport polymer with Formula I, Ar³has Formula d

Here; R⁹ is the same or different at each occurrence and is selectedfrom the group consisting of D, alkyl, alkoxy, siloxane, silyl, ester,deuterated alkyl, deuterated alkoxy, deuterated siloxane, deuteratedester, and deuterated silyl, wherein adjacent R⁹ groups can be joinedtogether to form a fused ring. Also; p is the same or different at eachoccurrence and is an integer from 0-4, q is an integer from 0-5, and ris an integer from 1 to 5. R⁹ may also be an alkyl or deuterated alkylgroup with p=0, and q=r=1.

In some embodiments of the hole transport polymer with Formula I, a>0and R¹ is D or C₁₋₁₀ alkyl. The C₁₋₁₀ alkyl group may also bedeuterated. Alternatively, a>0 and R1 is D or C₆₋₂₀ aryl, and this arylgroup may be deuterated.

In some embodiments of the hole transport polymer with Formula I, n>5.Some specific embodiments of the hole transport polymer with Formula Iare

This disclosure also includes an organic electronic device comprising ananode, a cathode, and at least one organic active layer therebetween,wherein the organic active layer comprises a hole transport polymerhaving Formula I.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.The use of numerical values in the various ranges specified herein isstated as approximations as though the minimum and maximum values withinthe stated ranges were both being preceded by the word “about.” In thismanner, slight variations above and below the stated ranges can be usedto achieve substantially the same results as values within the ranges.

Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum average valuesincluding fractional values that can result when some of components ofone value are mixed with those of different value. Moreover, whenbroader and narrower ranges are disclosed, it is within thecontemplation of this invention to match a minimum value from one rangewith a maximum value from another range and vice versa.

What is claimed is:
 1. A hole transport polymer having a carbazole groupand an amino nitrogen, wherein said hole transport polymer has Formula Ior Formula II

wherein: Ar¹, Ar², and Ar⁴ are the same or different and are substitutedor unsubstituted aryl groups or deuterated aryl groups; Ar³ issubstituted or unsubstituted aryl groups or deuterated aryl groups; E isthe same or different at each occurrence and is selected from the groupconsisting of H, D, halide, alkyl, aryl, siloxane, deuterated alkyl,deuterated aryl, deuterated siloxane, and a crosslinking group; R¹-R²are the same or different at each occurrence and are selected from thegroup consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl,amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy,deuterated alkyl, deuterated partially-fluorinated alkyl, deuteratedaryl, deuterated heteroaryl, deuterated amino, deuterated silyl,deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuteratedfluoroalkoxy, deuterated siloxane, deuterated siloxy, and crosslinkinggroups, wherein adjacent groups selected from R¹ and R² can be joinedtogether to form a fused ring; a is an integer from 0-4; b is an integerfrom 0-3; and n is an integer greater than or equal to 1;

wherein: Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or differentand are substituted or unsubstituted aryl groups or deuterated arylgroups; Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups ordeuterated aryl groups; E is the same or different at each occurrenceand is selected from the group consisting of H, D, halide, alkyl, aryl,siloxane, deuterated alkyl, deuterated aryl, deuterated siloxane, and acrosslinking group; R¹-R² are the same or different at each occurrenceand are selected from the group consisting of D, F, CN, alkyl,fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, alkoxy, aryloxy,fluoroalkoxy, siloxane, siloxy, deuterated alkyl, deuteratedpartially-fluorinated alkyl, deuterated aryl, deuterated heteroaryl,deuterated amino, deuterated silyl, deuterated germyl, deuteratedalkoxy, deuterated aryloxy, deuterated fluoroalkoxy, deuteratedsiloxane, deuterated siloxy, and crosslinking groups, wherein adjacentgroups selected from R¹ and R² can be joined together to form a fusedring; b is an integer from 0-3; and n is an integer greater than orequal to1;
 2. A hole transport copolymer having Formula III

wherein: A is a monomeric unit having Formula Ia or Formula IIa;

wherein: Ar¹, Ar², and Ar⁴ are the same or different and are substitutedor unsubstituted aryl groups or deuterated aryl groups; Ar³ issubstituted or unsubstituted aryl groups or deuterated aryl groups;R¹-R² are the same or different at each occurrence and are selected fromthe group consisting of D, F, CN, alkyl, fluoroalkyl, aryl, heteroaryl,amino, silyl, germyl, alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy,deuterated alkyl, deuterated partially-fluorinated alkyl, deuteratedaryl, deuterated heteroaryl, deuterated amino, deuterated silyl,deuterated germyl, deuterated alkoxy, deuterated aryloxy, deuteratedfluoroalkoxy, deuterated siloxane, deuterated siloxy, and crosslinkinggroups, wherein adjacent groups selected from R¹ and R² can be joinedtogether to form a fused ring; a is an integer from 0-4; b is an integerfrom 0-3; # is a point of attachment to other monomeric units; B is amonomeric unit having at least three points of attachment in thecopolymer; E is the same or different at each occurrence and is selectedfrom the group consisting of H, D, halide, alkyl, aryl, arylamino,siloxane, crosslinkable groups, deuterated alkyl, deuterated aryl,deuterated arylamino, deuterated siloxane, and deuterated crosslinkablegroups;

wherein: Ar¹, Ar², Ar^(2a), Ar⁴, and Ar^(4a) are the same or differentand are substituted or unsubstituted aryl groups or deuterated arylgroups; Ar³ and Ar^(3a) are substituted or unsubstituted aryl groups ordeuterated aryl groups; R¹-R² are the same or different at eachoccurrence and are selected from the group consisting of D, F, CN,alkyl, fluoroalkyl, aryl, heteroaryl, amino, silyl, germyl, ester,alkoxy, aryloxy, fluoroalkoxy, siloxane, siloxy, deuterated alkyl,deuterated partially-fluorinated alkyl, deuterated aryl, deuteratedheteroaryl, deuterated amino, deuterated silyl, deuterated germyl,deuterated ester, deuterated alkoxy, deuterated aryloxy, deuteratedfluoroalkoxy, deuterated siloxane, deuterated siloxy, and crosslinkinggroups, wherein adjacent groups selected from R¹ and R² can be joinedtogether to form a fused ring; b is an integer from 0-3; # is a point ofattachment to other monomeric units; and x, y, and z are the same ordifferent and are mole fractions, such that x+y+z=1, and x and y arenon-zero.
 3. The hole transport polymer according to claim 1, in whichAr¹-Ar⁴ are aryl groups at least one of which is further substitutedwith additional groups.
 4. The hole transport polymer according to claim3, in which the additional groups on the aryl groups are alkyl groupshaving 1 to 6 carbon atoms.
 5. The hole transport polymer according toclaim 1, in which at least one of a and b does not equal zero.
 6. Thehole transport polymer according to claim 1, in which n>10.
 7. The holetransport copolymer according to claim 2, in which Ar¹-Ar⁴ are arylgroups at least one of which is further substituted with additionalgroups.
 8. The hole transport copolymer according to claim 2, in whichthe molar ratio of A+B to E is in the range of 50:50 to 90:10.
 9. Thehole transport polymer or copolymer as in any preceding claim, in whichthe hole transport polymer or copolymer contains at least one D.
 10. Anorganic electronic device comprising an anode, a cathode, and at leastone organic active layer therebetween, wherein the organic active layercomprises a hole transport polymer or copolymer according to anypreceding claim.